Single‐Atom Catalysis in Organic Synthesis

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(34)

Published: March 15, 2023

Single-atom catalysts hold the potential to significantly impact chemical sector, pushing boundaries of catalysis in new, uncharted directions. These materials, featuring isolated metal species ligated on solid supports, can exist many coordination environments, all which have shown important functions specific transformations. Their emergence has also provided exciting opportunities for mimicking metalloenzymes and bridging gap between homogeneous heterogeneous catalysis. This Review outlines impressive progress made recent years regarding use single-atom organic synthesis. We illustrate knowledge gaps search more sustainable, earth-abundant synthetic applications.

Language: Английский

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Single-atoms Ru/NiFe layered double hydroxide electrocatalyst: Efficient for oxidation of selective oxidation of 5-hydroxymethylfurfural and oxygen evolution reaction

Applied Catalysis B Environment and Energy, Journal Year: 2023, Volume and Issue: 339, P. 123157 - 123157

Published: Aug. 7, 2023

Language: Английский

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Boosting the Hydroformylation Activity of a Rh/CeO₂ Single-Atom Catalyst by Tuning Surface Deficiencies

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(11), P. 7243 - 7255

Published: May 15, 2023

Controlling the interactions between atomically dispersed metal atoms and support plays significant roles in determining activity selectivity of single-atom catalysts. In this report, we tuned local coordination environment Rh single on CeO2 via calcination to construct a highly active hydroformylation catalyst. Single-atom Rh/CeO2 calcined at high temperature exhibits more oxygen vacancies, which lead formation large amount low-coordination species that are for hydroformylation. Under optimum conditions, best catalyst achieved TOF approximately 5000 h–1 with 100% aldehyde propylene butanal. situ FTIR spectroscopy XPS characterizations provide strong evidence 800 °C-calcined is easily activated form surface HRh(CO)2 species, favoring adsorption CO insertion. This work highlights significance engineering metal–support tuning performance catalysts contributes mechanistic insights into Rh-catalyzed reactions.

Language: Английский

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Suppressing Metal Leaching and Sintering in Hydroformylation Reaction by Modulating the Coordination of Rh Single Atoms with Reactants

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(17), P. 11955 - 11967

Published: April 19, 2024

Hydroformylation reaction is one of the largest homogeneously catalyzed industrial processes yet suffers from difficulty and high cost in catalyst separation recovery. Heterogeneous single-atom catalysts (SACs), on other hand, have emerged as a promising alternative due to their initial activity reasonable regioselectivity. Nevertheless, stability SACs against metal aggregation leaching during has rarely been addressed. Herein, we elucidate mechanism Rh by investigating structural evolution

Language: Английский

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Structure–Reactivity Relationship of Zeolite-Confined Rh Catalysts for Hydroformylation of Linear α-Olefins

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 9, 2025

Substituting the molecular metal complexes used in industrial olefin hydroformylation process is of great significance fundamental research and practical application. One major difficulties replacing classic catalysts with supported low chemoselectivity regioselectivity because lack a well-defined coordination environment active sites. In this work, we have systematically studied influences key factors (crystallinity, alkali promoters, etc.) Rh-MFI zeolite on their performances for long-chain α-olefins (LAOs). With help comprehensive spectroscopy electron microscopy characterization results, can correlate structural features various catalytic performances. The resultant structure–reactivity relationship guides us to prepare nanosized catalyst, which exhibits about 3-fold improvement specific activity compared catalyst conventional crystallite sizes maintains very high LAOs.

Language: Английский

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Rhodium Single‐Atom Catalyst Design through Oxide Support Modulation for Selective Gas‐Phase Ethylene Hydroformylation

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(1)

Published: Oct. 31, 2022

A frontier challenge in single-atom (SA) catalysis is the design of fully inorganic sites capable emulating high reaction selectivity traditionally exclusive organometallic counterparts homogeneous catalysis. Modulating direct coordination environment SA sites, via exploitation oxide support's surface chemistry, stands as a powerful albeit underexplored strategy. We report that isolated Rh atoms stabilized on oxygen-defective SnO2 uniquely unite excellent TOF with essentially full gas-phase hydroformylation ethylene, inhibiting thermodynamically favored olefin hydrogenation. Density Functional Theory calculations and characterization suggest substantial depletion catalyst lattice oxygen, energetically facile , key to unlock pliability at mononuclear centers, leading an exceptional performance which par molecular catalysts liquid media.

Language: Английский

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Low-temperature hydroformylation of ethylene by phosphorous stabilized Rh sites in a one-pot synthesized Rh-(O)-P-MFI zeolite

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Nov. 7, 2023

Zeolites containing Rh single sites stabilized by phosphorous were prepared through a one-pot synthesis method and are shown to have superior activity selectivity for ethylene hydroformylation at low temperature (50 °C). Catalytic is ascribed confined Rh2O3 clusters in the zeolite which evolve under reaction conditions into Rh3+ sites. These effectively Rh-(O)-P structure using tetraethylphosphonium hydroxide as template, generates situ phosphate species after H2 activation. In contrast Rh2O3, Rh0 appear less active propanal production ultimately transform Rh(I)(CO)2 similar conditions. As result, we show that it possible reduce of with solid catalyst down 50 °C, good high selectivity, controlling electronic morphological properties

Language: Английский

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Adjacent MnOx clusters enhance the hydroformylation activity of rhodium single-atom catalysts

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: 350, P. 123923 - 123923

Published: April 24, 2024

Language: Английский

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A one-pot strategy for anchoring single Pt atoms in MOFs with diverse coordination environments

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(9), P. 1158 - 1167

Published: June 20, 2024

Language: Английский

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Rational Design Principles of Single-Atom Catalysts in Hydrogen Production and Hydrogenation

Energy & Environmental Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

This review summarizes the research progress of single-atom catalysts (SACs) in hydrogen production and hydrogenation, proposes rational design principles SACs for hydrogenation firstly.

Language: Английский

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